In the drive for higher integration and operating speeds in LSI devices, the pattern rule is made drastically finer. The rapid advance toward finer pattern rules is grounded on the development of a projection lens with an increased NA, a resist material with improved performance, and a light source with a shorter wavelength.
Resist materials adapted for KrF excimer laser (248 nm) started use on the 0.3 μm process and entered the mass production phase on the 0.13 μm rule. A wavelength change-over from KrF to shorter wavelength ArF excimer laser (193 nm) is expected to enable miniaturization of the design rule to below 0.13 μm. Since commonly used novolak resins and polyvinylphenol resins have very strong absorption in proximity to 193 nm, they cannot be used as the base resin for resists. To ensure transparency and dry etch resistance, acrylic resins and alicyclic (typically cycloolefin) resins are investigated, leading to mass-scale production of devices by the ArF lithography.
For the next 45-nm node devices which required an advancement to reduce the wavelength of exposure light, the F2 lithography of 157 nm wavelength became a candidate. However, for the reasons that the projection lens uses a large amount of expensive CaF2 single crystal, the scanner thus becomes expensive, hard pellicles are introduced due to the extremely low durability of soft pellicles, the optical system must be accordingly altered, and the etch resistance of resist is low; the F2 lithography was postponed and instead, the early introduction of ArF immersion lithography was advocated. This enables mass-scale production of 45-nm node devices. For the mass-scale production of 32-nm node devices, the double patterning process utilizing sidewall spacer technology is used although the process suffers from complexity and length.
For the purpose of increasing the throughput of an ArF immersion lithography tool, an attempt is made to increase the scanning rate of the scanner. To this end, it is necessary to improve water slip on the surface of a resist film in contact with immersion water. Patent Documents 1 and 2 disclose a liquid immersion resist composition to which a fluorinated additive is added to increase water repellency on resist surface. Although a water repellent polymer is mixed with a base resin, acid generator and other components in a resist composition, the polymer will segregate, after spin coating, on the resist surface to improve water repellency. Another advantage of the water repellent polymer is that by virtue of fluoroalcohol groups, it dissolves in alkaline developer, causing few defects after development. To compensate for a lowering of productivity by double patterning, stepper manufacturers make efforts to accelerate the scanning rate of the scanner. It is thus necessary to further improve water repellency on the resist surface.
For the fabrication of sub-32-nm node devices, the onset of extreme ultraviolet (EUV) lithography using an exposure wavelength of 13.5 nm which is shorter than the conventional lasers by one order of magnitude and thus featuring improved resolution is expected rather than the double patterning process with noticeable costs.
In the EUV lithography, a low laser power and light attenuation by reflecting mirror lead to a reduced quantity of light. Then light with a low intensity reaches the wafer surface. It is urgently demanded to develop a high-sensitivity resist material in order to gain a throughput despite a low light quantity. However, a trade-off relationship of sensitivity is pointed out that the sensitivity of resist material can be increased at the sacrifice of resolution and edge roughness (LER, LWR).
For the purpose of suppressing outgassing from a resist film during EUV exposure, Patent Document 3 proposes to add a copolymer comprising fluoroalcohol-containing recurring units and aromatic group-containing recurring units to a resist composition. After spin coating, the copolymer will segregate on the resist surface so that the aromatic groups serve to shut out outgassing from the resist film.
Patent Document 4 proposes spin coating of a resist composition in a solvent atmosphere. Patent Document 5 discloses prebaking of a spin-coated resist in a solvent atmosphere under reduced pressure. In either of these methods, the resist composition may be coated by dispensing a small amount thereof, and the resulting resist film is improved in flatness.
Studies are made on a patterning process utilizing the direct self-assembly (DSA) phenomenon of a block copolymer. For DSA, heating above 200° C. for several hours is necessary. For attaining DSA within a short time, heating in a solvent atmosphere is effective. As the solvent penetrates into the block copolymer, the polymer is improved in mobility so that the rate of DSA is accelerated.